Dyestuff of the isodibenzanthrone series



Patented Mar. 12, 1929.

UNlTED snares- TD GRASSELLI DYEST'UFF GURPOBATIU DELAWARE.

ear-ear series.

HEINRICH NERESHEEHIER, LUDWIGS- FF, 0F MANNHEIM, GERMMIY, ASSIGNORS N, 9F NEW YQRK, N. Y., A @URIQRATIQN 0F DYESTUFF @F THE ISOIDFZBENZANTHRUNE SERIES.

No Drawing. flriginal application filed ()ctober 16, 1925, serial Filo. 62,934, and in Germany @ctober 25,

1924. Divided and this application filed December 9,

The subject matter of this application has been divided out from our copending application Serial No. 62,934, filed October 16, 1925, with the express intention to apply for this divisional application.

As we have shown in our said parent application, new members of the class of isodibenzanthrones can be obtained by condensation with the aid of alkaline condensing agents of mixtures of Bzl-halogen-benzanthrones and benzanthrone itself or such derivatives thereof as possess a free Bzlposition. Generally, about equiinolecular amounts of the Bzl-halogen compound and the llzl-unsubstituted compound Will be chosen, but an excess ofthe Bzl-halogen-benzanthrone may also be employed. Various alkaline condensing agents suitable for offecting condensations of the kind in question may be used, but

condensing medium we mention mixtures of caustic alkalis and alkali metal alcoholates in the presence of an inert diluent. Such mixtures can be readily prepared from a caustic alkali and a restricted quantity of an alcohol, and the benzanthrone bodies and the diluent may already be present when mixing the alkali and alcohol. ()Xygen should be excluded as far as possible, to which end a current of an inert gas is passed through the mixture or Vessel during the reaction. Very good yields are also obtained with metal arylides as condensing agents. In all cases the benzanthrone as well as the Bzl-halogen-benzanthrone body must also contain the 2-position unsubstituted.

The said process permits of obtaining allso unsymrnetrically substituted isodibenzanthrones by starting from a benzanthrone and a Bzl-halogen-benzanthr0ne, only one of which contains a further substituent, or which contain dill-erent substitutents, or the same substituents, but in different positions.

lsodibenzanthrones can also be obtained by subjecting the intermediary products of the as a particularly suitable 1926. Serial No. 153,724.

to the action of condensing agents of an alkallne or acid nature. Such agents may at the same time be halogenating agents when in some cases halogenated dyestuffs will be obtained.

The aforesaid invention is more fully explained by the following examples to which however the invention is not limited. The parts are by weight.

Example .2.

10 parts of 2.Bzl-dibenzanthronyl lorepa-red for example in accordance with EX- amples 1 and 3 of application Serial No. 62,934, filed October 16, 1925, are added at about 125 (3. to a suspension of sodium anilide in aniline prepared from 3 parts of metallic sodium and 200 parts of dryaniline in i to .troducing a current a current of nitrogen. The mixture is heated to 140 to 150 C. until the formation of dyestufi' is finished. When cool, the blue violet coloured mass is poured into dilute hydrochloric acid. The isodibenzanthrone precipitated is filtered off, Washed and dried and maybe purified by boiling with organic solvents. It corresponds to the formula and forms a dark powder of met llic lustre which dissolves in concentrated su furic acid pure green. 1

i E wample 2.

10 parts of 2.Bzl-dibenzanthronyl are slowly introduced at about from 130 to 135 G. into a solution of 40 parts of caustic potash in 40 parts of absolute alcohol, care being taken that the temperature does not exceed 135 C. The mixture is then kept at from 135 to 140 C. for about half an hour, poured into water and boiled while inof air until all of the dyestuff is precipitated. It is filtered off, washed and dried. Pure isodibenzanthrone is obtained in a nearly theoretical yield.

When using G-meth l-2.Bzl'-dibenzanthronyl (see Example 2 0 application Serial No. 62,934), instead of 2.Bzl-dibenzanthronyl, 6-methyl-isodibenzanthrone corresponding to the formula is obtained which dyes cotton more bluishshades than isodibenzanthrone.-

6-ohlor-2.Bzl'-dibenzanthronyl may be used in the same manner forming (i-chlorisodibenzanthrone is isodibenzanthrone corresponding to the formula which dyes cotton considerably bluer and stronger shades than isodibenzanthrone.

Emample 3.

A mixture of 3 parts of 2.Bzl-dibenzanthronyl with 20 parts of, anhydrous ferric chlorid and 15 parts of dry common salt is heated to about 250 C. until a test portion of the mass, after being treated with dilute hydrochloric acid, is totall soluble to a vat. The dyestuff so obtaine contains chlorine and dyes the fibre from a blue vat strong blue violet shades. I

WVith aluminium chlorid instead of ferric chlorid, at about 300 C. isodibenzanthrone is obtained. The latter can also be prepared by heating 2.Bzl-dibenzanthronyl with sulfuric acid of per cent strength in the presence of mercury salts.

E mample 4.

cohol, a'mixture of 13 parts of Bzl-brombenzanthrone and 7 parts of bcnzanthrone is introduced while stirring and the said tent perature kept for 3 hours. The blue mass is boiledwith a large quantity of water and an addition of sodium'hydrosulfite and the resulting blue vat filtered and the dyestufi' precipitated by means of air. Practically pure obtained.

When employing a mixture Bzl-brom-benzanthrone and 10 parts of 6-chlor-benzanthrone (see Berichte der Deutschen Chemischen Gesellschaft, vol. 55, page 114) in the same manner, 6-chlor-isodibenzanthrone as described in Example 2, third paragraph, is obtained.

of 10 parts of E mample 5.

added to the suspension while stirring well boiling it with organic solvents, for example and, if necessary, while cooling. When the acetone, nitrobenzene and the like. sodium is dissolved, 70 parts of finely pul- The reaction may also be carried out at a verized cautic potash and then, while carehigher or lower temperature. In the latter fully excluding air, 12 parts of pure Bzlcaseffor example at to 0., 6-chlorchlor-benzanthrone and 8 parts of pure benisodibenzanthrone and 6-ehlor-2.Bzl-dilienm zanthrone are added. The mixture is grad zanthronyl are formed simultaneously. ually heated to to C. and stirred at Exam Z6 9 this temperature until the violet blue color p of the paste becomes no longer darker and is By the condensation of 6-Bzl-d1cl1lor-benthen treated with steam in order to drive zanthrone (which may be obtained by treat- 5 oil xylene and alcohol. Isodibenzanthrone is ing fi-chlor-benzanthrone with sulfuryl chloobtained in much better yield than when emrid and forms yellow needles melting at ploying all of the benzanthrone in the form 262 to 264 C. and which by the oxidation of the Bzl-chlor derivative. with chromic acid forms a chlor-anthrainstead of benzanthrone fi-methylquinone carboxylic acid the amide of which go benzanthrone (see Annalen, VOl. 394, ,page can be transformed in the usual manner into 147) is used, G-methyldsodibenzanthrone is 1 amino-6chloranthraquinone) with benobtained (see Example 2). zanthrone by means of sodium anilide, 6-

ehlor-isodibcnzanthrone is also obtained.

Example 6. 30 parts of isopropyl alcohol are added at Ewampze 19 to 15 (1., while stirring and excluding A mixture of 12 parts of 6-b'rom-Bzl-chloran), to a lnixtureof 300 parts of benzen 70 benzanthrone (yellow needles melting at 254 parts of powdered caustic potash, 11 parts of to 255 C. which can be prepared by treating pure Bzl-chlor-benzanthroneand 9 parts of ZI- hI I W h i IB r so pure benzanthrone. After stirring the mixfr -b1'0 -benZant-h ne and sulfuryl ture for some hours, and driving oil" th s lchlorid) and 8 parts of benza'nthrone, when vent, the dyestuff can be obtained in the man- Treated in a mi r mann r, giWBS aviolet ned described in Example 4. blue vat dyestuif consisting substantially of b Mixtglres of Bzl-chldr-benzanthrone and G-broni-isodibenzanthrone. o5

enzant rone ma also be repared b artially chlorinating benzantl irone. y p Ewampze By treating a mixture of 8-ehlor-benzan throne (yellow needles melting at 174 C. While stiri ingand excluding air "as far as which may be prepared by fractional crystal- Ewample 7,.

l0 possible, 24 parts of ethyl alcohol are added l zation of the product obtained by the reaca to a suspension consisting of 300 parts of ben- 1 1 f glyce l and Sulfuric acid on l-chl0r- Zeno, 70 parts of finely pulverized caustic p0t anthraquinone in the presence of aniline sulash, 11 parts of Bzl-chlor-benzanthrone (Fp fate S- atent ,894) and Which 176 see U. S. Patent 906,367) and 9 parts of when Oxidized forms a chlor-anthraquinone G-chlor-benzanthrone, at 70 to 75 C. and Carboxylic acid capable of being transformed stirred at this temperature for one to two o 1 m qu nd 1- more' hours. After driving ofl" the solvent, Chlor-benzanthrone with sodium anilide in the product is dissolved in water whereby a the manner described in Example 8, 8-chlorblue solution is formed from which the dyeisodibenzanthrone corresponding to the for- 1w stufi is precipitated by means of a current of mula air. A dyestufi' practically identical with that I of Example 2, third paragraph, is obtained in i1 a very good yield. 5

Example 8.

An intimate mixture of 10 parts of Bzlchlor-benzanthrone and 10 parts of 6-chlorbenzanthrone is introduced while stirring at 70 G. into a mixture of 15 parts of sodium 7 anilide and 200 parts of dry aniline in a cur- 6 about 90 C. and is kept at this height until the formation of the dyestuff is finished. The mass is then poured into dilute hydrois obtained which dyes cotton from the vat chlorio acid whereupon the brown red prevery fast strong reddish Violet shades.

eip1tate 1s filtered off, washed and dried. The Instead of 8-chlor-benzanthrone and Bzl- 6-ehlor-1sod1benzanthrone may be purifiedby chlor-loenzanthrone, a mixture of benzanthrone'and 8.Bzl-dichlor-benzanthrone (yellow needles melting at 218. to 220 C. prepared from 8-chlor-benzanthrone1and sul furyl chlorid) may be used as Well.

I E acrimple 12.

By condensing a mixture of 10 parts of 8.Bzl-dichlor-benzanthrone and 9 parts of 8- chlor-benzanthrone in the manner described in Example 8, 8.8-dichlor-isodibenzanthrone corresponding to the formula is obtained which dyes cotton still more reddish shades than 8-chlor-isodibenzanthrone.

1 As new articles of manufacture, isodi benzanthrones containing at least one substitnent free fromhnitrogen but not more than one halo en radical in the molecule unless a non-halo1d substituent is present.

2. As new articles of manufacture, monohalogen-isodibenzanthrones,

dissolving 1n condensing agent until concentrated sulfuric acid with a green coloration and giving with alkaline hydrosulfite solution a blue Vat from which cotton is dyed reddish violet to violet blue shades.

3. As new articles of manufacture, G-chlorisodibenzanthrone containing between about 6 per cent to 7 per cent of chlorine, dissolving in concentrated sulfuric acid with a green coloration, and in alkaline hydrosulfite solution to a blue vat from which cotton is 'dyed violet blue shades,

4. The process of manufacturing vat coloring matters of the benzanthrone series which consists in treating a mixture of a benzanthrone body, not substituted in 2- and in Bzlposition with a Bzl-halogen benzanthrone body with a free 2-position, with an alkaline the formation of dyestuff has taken place;

5. The process of manufacturing vat co1oring matters of the benzanthrone series which consists in condensing the intermediary product of an incomplete alkaline condensation of about equimolecular proportions of a benzanthrone body with free 2 and .Bzl-positions and a Bzl -halogen-benzanthrone with free 2-position, said intermediary product having still free Bzland Q-Positions, with an alkaline condensing agent until a vat coloring matter is produced.

In testimony whereof we have hereunto set our hands.

ARTHUR LUTTRINGHAUS. HEINRICH NERESHEIMER.

. HUGO WOLFF. 

